CN102332499A - Method for utilizing microparticles to produce double-textured transparent electrode - Google Patents
Method for utilizing microparticles to produce double-textured transparent electrode Download PDFInfo
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- CN102332499A CN102332499A CN201110296366A CN201110296366A CN102332499A CN 102332499 A CN102332499 A CN 102332499A CN 201110296366 A CN201110296366 A CN 201110296366A CN 201110296366 A CN201110296366 A CN 201110296366A CN 102332499 A CN102332499 A CN 102332499A
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Abstract
The invention relates to a method for utilizing microparticles to produce a double-textured transparent electrode, which belongs to the technical field of transparent conductive oxide films. In the technical scheme, a layer of microparticles are first coated on a glass substrate, a film deposition technology is then adopted to produce a TCO (transparent conductive oxide) film with certain thickness, the surface of the film presents a rugged texture structure like the coated microparticles, the feature size of the film corresponds to the size of the covered microparticles, and a wet etching method is utilized to etch the surface of the TCO film to a certain degree. A texture structure with a certain shape can be obtained by changing the technological parameters of etching, the feature size of the texture structure is smaller than the feature size of the microparticles, and thereby the whole transparent electrode is provided with double texture structures; or the TCO film with a texture structure is directly grown on the surface of the coated microparticles, and thereby the whole transparent electrode is provided with the double texture structures; and the transparent electrode is applied to film solar cells, and can effectively scatter both visible light and near-infrared light.
Description
Technical field
The present invention relates to a kind of method of utilizing microparticle to prepare double structure matte transparency electrode, particularly be fit to the preparation method of the transparent conductive film of thin film solar cell application, belong to the transparent conductive oxide film technical field.
Background technology
Get into 21st century, the mankind become increasingly conspicuous to the contradiction of the limited supply of volatile growth of energy demand and fossil energy, and the whole world is growing more intense around the competition of the energy.Solar energy is described as optimal green energy resource, is inexhaustible, nexhaustible clean energy resource, and as one of effective means that solar energy is utilized, the application prospect of solar cell is very wide.Solar cell has mainly comprised crystal silicon battery and hull cell (silicon-base thin-film battery, cadmium telluride battery (CdTe), CIGS battery (CIGS)).Silicon-base thin-film battery is because its relative mature technique and advantages such as excellent high and low light level performance, thereby obtained great development.The basic structure of thin film silicon solar cell (shown in Figure 1) generally comprises: glass substrate 1, transparent preceding electrode 2, silicon thin film photoelectric conversion layer 3, back reflector 4, encapsulating material 5 and back of the body glass 6 etc.; Thin film solar cell is as an optical system; Thereby improve its utilance and improve conversion efficiency, need carry out appropriate design each layer of battery component optical thin film to sunlight.Wherein, Electrode 2 need possess high optical transmittance, high conductivity and incident light 7 is had stronger scattering power before transparent; Thereby improve the absorption of battery to light; Increase photogenerated current, improve battery conversion efficiency, the performance of transparent preceding electrode 2 improves and the industrialization Study on Preparation Technology is one of focus of current thin film solar cell research and development.TCO film as preceding electrode in the thin film silicon solar cell generally has matte texture, and purpose is scattering power (shown in Figure 2), the light path of prolongation light in the intrinsic absorbed layer that improves incident light, improves the absorption of battery to light.The surface suede structure depends on the characteristic size that it has to the scattering of light ability of different-waveband scope; As the surperficial matte texture that has than small-feature-size mainly has stronger light scattering effect to the 400-700nm wave band in the visible spectrum, and the surperficial matte texture that has than large-feature-size (like 1--2 μ m) partly has stronger light scattering effect to the near-infrared in the spectrum.Realize effective absorption of 400-1200nm spectral region, will have less and bigger two kinds of matte texture and combine that forming double structure matte (shown in Figure 3) is more satisfactory selection.How preparing the matte TCO film with double structure, expand the TCO film to different-waveband scattering of light ability, widen the utilize scope of battery to solar spectrum, is one of key technology that improves the hull cell conversion efficiency.
Summary of the invention
The object of the invention provides a kind of method of utilizing microparticle to prepare double structure matte transparency electrode, simultaneously visible light and near infrared light is played good light scattering effect, strengthens the utilize ability of battery to solar spectrum, solves the problems referred to above that background technology exists.
Technical scheme of the present invention is:
A kind of method of utilizing microparticle to prepare double structure matte transparency electrode comprises following processing step:
(1) on glass substrate, applies one deck microparticle;
(2) adopt film deposition techniques to prepare the TCO film; Transparent conductive oxide (Transparent conductive Oxide; Be called for short TCO) film; When microparticle was covered fully, film surface appeared and applies the identical ups and downs suede structure of microparticle, and its characteristic size is corresponding with the microparticle size that is covered;
(3) utilize the method for wet etching that etching is carried out on its surface, obtain matte texture through changing the etching technics parameter, its characteristic size is little than the microparticle characteristic size, makes whole transparency electrode have the matte texture of double structure; Or have the TCO film of texture structure in the particle surface direct growth that applies, and make whole transparency electrode have the matte texture of double structure, be applied to thin-film solar cells, all can realize effective light scattering to visible light and near infrared light.
The microparticle that applies is the semiconductor grain with broad-band gap, comprises TiO
2, SiO
2With the ZnO material, particle size is at 500--900nm, grain spacing 0--10 μ m.
On above-mentioned matte TCO film with double structure, prepare hull cell; With the silicon-based film solar cells is example; Step is following: utilize plasma enhanced chemical vapor deposition deposition techniques amorphous silicon p-i-n or amorphous silicon p-i-n/ microcrystal silicon p-i-n lamination or tie photoelectric conversion layers such as p-i-n structure more; Utilize magnetron sputtering or low-pressure chemical vapor deposition or spin coating technique to prepare back electrode ZnO or ZnO/Al or ZnO/Ag or Ag; After electrode welding, lead packages technology, obtain hull cell.
The TCO film deposition techniques that is adopted is LPCVD technology, magnetron sputtering technique, pulsed laser deposition technique, spin coating technique.
The TCO transparent conductive film of indication is zinc oxide (ZnO) film; Boron (B) is ZnO thin film doped, aluminium (Al) is ZnO thin film doped, gallium (Ga) is ZnO thin film doped, other doped with metal elements and codope ZnO film, also can be the SnO 2 thin film of doped with metal elements.
Said change etching technics parameter comprises the speed that kind, concentration, temperature, etch period, the TCO glass of etching solution move in solution.
Said glass substrate is a glass substrate, comprises half tempered glass substrate, toughened glass substrate.
Beneficial effect of the present invention: no matter be size, the spacing of microparticle in the technology of the present invention 1); Or the deposition process parameters of transparency electrode; Perhaps the parameter of etching technics all can be regulated in the larger context; Thereby obtain the double structure matte of different size, realize coupling with the corresponding spectral response range of variety classes thin-film solar cells.2) the matte transparency electrode of the double structure among the present invention has been widened the spectral region of light scattering, and the hull cell that on the matte transparency electrode of this double structure, prepares can improve light absorption and utilance, thereby can improve the conversion efficiency of solar cell.
Description of drawings
Fig. 1 has provided film solar battery structure sketch map (is example with the thin-film silicon cell);
Fig. 2 is the sketch map of preceding electrode of TCO and sunken light action thereof;
Fig. 3 is a double structure matte sketch map;
Fig. 4 is a specific embodiment of the invention sketch map;
Among the figure: glass substrate 1, transparent preceding electrode 2, silicon thin film photoelectric conversion layer 3, back reflector 4, encapsulating material 5, back of the body glass 6, incident light 7, microparticle 8, TCO film 9, transparency electrode 10.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described further through embodiment.
Embodiment one
1, adopts the method for chemical spin coating, the microparticle (8) of certain size (for example 600nm) is coated to glass substrate (1) surface;
2, adopt the method deposition thick ZnO film of 1000nm (9) of magnetron sputtering, deposition power 3KW, 320 ℃ of underlayer temperatures, deposition pressure 5mTorr, gas flow 20sccm; Film demonstrates and applies the identical concaveconvex structure of microparticle, characteristic size identical with coated particle (8) (for example 600nm);
3, utilize the method for wet etching that etching is carried out on ZnO film (9) surface; The speed that kind (for example watery hydrochloric acid), concentration (for example concentration of volume percent is 0.5%), temperature (for example room temperature), etch period (for example 45s), TCO glass through selective etching solution moves in solution (for example; 10mm/s) wait technological parameter to obtain to have the matte texture of definite shape; Its characteristic size less (for example 300nm); Make whole transparency electrode (10) have the matte texture of double structure, be applied to thin-film solar cells, all can realize effective light scattering visible light and near infrared light.
Embodiment two
As implement a described method, go up in glass substrate (1) and apply preparation one deck microparticle (8) film;
Adopt the method for LPCVD, have boron doping zinc-oxide (ZnO:B) film of texture structure, make whole transparency electrode (10) have the matte texture of double structure in the superficial growth of coated particle.
Claims (7)
1. method of utilizing microparticle to prepare double structure matte transparency electrode is characterized in that comprising following processing step:
1. go up in glass substrate (1) and apply one deck microparticle (8);
2. adopt film deposition techniques to prepare TCO film (9), when microparticle was covered fully, film surface appeared and applies the identical ups and downs suede structure of microparticle, and its characteristic size is corresponding with the microparticle size that is covered;
3. utilize the method for wet etching that etching is carried out on its surface, obtain matte texture through changing the etching technics parameter, its characteristic size is little than the microparticle characteristic size, makes whole transparency electrode have the matte texture of double structure; Or have the TCO film of texture structure in the particle surface direct growth that applies, and make whole transparency electrode have the matte texture of double structure, be applied to thin-film solar cells, all can realize effective light scattering to visible light and near infrared light.
2. prepare the method for double structure matte transparency electrode according to the said microparticle that utilizes of claim 1, it is characterized in that the microparticle that applies is the semiconductor grain with broad-band gap, comprise TiO
2, SiO
2With the ZnO material, particle size is at 500--900nm, grain spacing 0--10 μ m.
3. prepare the method for double structure matte transparency electrode according to claim 1 or the 2 said microparticles that utilize; It is characterized in that preparing hull cell having on the matte TCO film of double structure; With the silicon-based film solar cells is example; Step is following: utilize plasma enhanced chemical vapor deposition deposition techniques amorphous silicon p-i-n or amorphous silicon p-i-n/ microcrystal silicon p-i-n lamination or tie photoelectric conversion layers such as p-i-n structure more; Utilize magnetron sputtering or low-pressure chemical vapor deposition or spin coating technique to prepare back electrode ZnO or ZnO/Al or ZnO/Ag or Ag, after electrode welding, lead packages technology, obtain hull cell.
4. prepare the method for double structure matte transparency electrode according to claim 1 or the 2 said microparticles that utilize; It is characterized in that said change etching technics parameter, comprise the speed that kind, concentration, temperature, etch period, the TCO glass of etching solution move in solution.
5. prepare the method for double structure matte transparency electrode according to claim 1 or the 2 said microparticles that utilize, it is characterized in that the TCO film deposition techniques that is adopted is LPCVD technology, magnetron sputtering technique, pulsed laser deposition technique, spin coating technique.
6. prepare the method for double structure matte transparency electrode according to claim 1 or the 2 said microparticles that utilize; The TCO transparent conductive film that it is characterized in that indication is zinc oxide (ZnO) film; Boron (B) is ZnO thin film doped, aluminium (Al) is ZnO thin film doped, gallium (Ga) is ZnO thin film doped, other doped with metal elements and codope ZnO film, also can be the SnO 2 thin film of doped with metal elements.
7. prepare the method for double structure matte transparency electrode according to claim 1 or the 2 said microparticles that utilize, it is characterized in that said glass substrate is a glass substrate, comprise half tempered glass substrate, toughened glass substrate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891216A (en) * | 2012-09-13 | 2013-01-23 | 中国科学院宁波材料技术与工程研究所 | Method for preparing dual-structure flocky ZnO-base transparent conductive thin film |
| CN103115448A (en) * | 2013-03-07 | 2013-05-22 | 日出东方太阳能股份有限公司 | Full-glass solar vacuum heat-collecting tube and preparation method thereof |
| CN103162452A (en) * | 2013-03-05 | 2013-06-19 | 日出东方太阳能股份有限公司 | Inoxidizability solar spectrum selective absorbing coating and preparation method thereof |
| CN106784060A (en) * | 2016-12-21 | 2017-05-31 | 蚌埠玻璃工业设计研究院 | A kind of zno-based transparent conducting glass with self-trapping smooth function |
| CN106784089A (en) * | 2016-12-21 | 2017-05-31 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of self-trapping smooth zno-based transparent conducting glass |
| CN109148611A (en) * | 2018-07-31 | 2019-01-04 | 江苏理工学院 | A method of enhancing copper indium gallium selenium solar cell efficiency using island silver nano-grain |
| CN110808299A (en) * | 2019-11-16 | 2020-02-18 | 中建材蚌埠玻璃工业设计研究院有限公司 | Flexible high-absorption rate thin film solar cell |
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| CN101572279A (en) * | 2009-06-10 | 2009-11-04 | 南开大学 | High mobility textured structure IMO/ZnO composite film grown by sputtering method and application thereof to solar cell |
| CN101692357A (en) * | 2009-10-13 | 2010-04-07 | 华东师范大学 | Method for preparing pile face doped zinc oxide transparent conductive film |
| US20110186120A1 (en) * | 2009-11-05 | 2011-08-04 | Guardian Industries Corp. | Textured coating with various feature sizes made by using multiple-agent etchant for thin-film solar cells and/or methods of making the same |
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Patent Citations (3)
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| CN101572279A (en) * | 2009-06-10 | 2009-11-04 | 南开大学 | High mobility textured structure IMO/ZnO composite film grown by sputtering method and application thereof to solar cell |
| CN101692357A (en) * | 2009-10-13 | 2010-04-07 | 华东师范大学 | Method for preparing pile face doped zinc oxide transparent conductive film |
| US20110186120A1 (en) * | 2009-11-05 | 2011-08-04 | Guardian Industries Corp. | Textured coating with various feature sizes made by using multiple-agent etchant for thin-film solar cells and/or methods of making the same |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891216A (en) * | 2012-09-13 | 2013-01-23 | 中国科学院宁波材料技术与工程研究所 | Method for preparing dual-structure flocky ZnO-base transparent conductive thin film |
| CN102891216B (en) * | 2012-09-13 | 2015-06-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing dual-structure flocky ZnO-base transparent conductive thin film |
| CN103162452A (en) * | 2013-03-05 | 2013-06-19 | 日出东方太阳能股份有限公司 | Inoxidizability solar spectrum selective absorbing coating and preparation method thereof |
| CN103162452B (en) * | 2013-03-05 | 2015-04-15 | 日出东方太阳能股份有限公司 | Inoxidizability solar spectrum selective absorbing coating and preparation method thereof |
| CN103115448A (en) * | 2013-03-07 | 2013-05-22 | 日出东方太阳能股份有限公司 | Full-glass solar vacuum heat-collecting tube and preparation method thereof |
| CN103115448B (en) * | 2013-03-07 | 2015-07-08 | 日出东方太阳能股份有限公司 | Full-glass solar vacuum heat-collecting tube and preparation method thereof |
| CN106784060A (en) * | 2016-12-21 | 2017-05-31 | 蚌埠玻璃工业设计研究院 | A kind of zno-based transparent conducting glass with self-trapping smooth function |
| CN106784089A (en) * | 2016-12-21 | 2017-05-31 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of self-trapping smooth zno-based transparent conducting glass |
| CN106784060B (en) * | 2016-12-21 | 2018-05-01 | 蚌埠玻璃工业设计研究院 | A kind of zno-based transparent conducting glass with self-trapping light |
| CN106784089B (en) * | 2016-12-21 | 2018-05-01 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of self-trapping smooth zno-based transparent conducting glass |
| CN109148611A (en) * | 2018-07-31 | 2019-01-04 | 江苏理工学院 | A method of enhancing copper indium gallium selenium solar cell efficiency using island silver nano-grain |
| CN110808299A (en) * | 2019-11-16 | 2020-02-18 | 中建材蚌埠玻璃工业设计研究院有限公司 | Flexible high-absorption rate thin film solar cell |
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